US2015706A - Process for making alkyl halides - Google Patents
Process for making alkyl halides Download PDFInfo
- Publication number
- US2015706A US2015706A US566321A US56632131A US2015706A US 2015706 A US2015706 A US 2015706A US 566321 A US566321 A US 566321A US 56632131 A US56632131 A US 56632131A US 2015706 A US2015706 A US 2015706A
- Authority
- US
- United States
- Prior art keywords
- halide
- mixture
- ether
- alkyl
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000001350 alkyl halides Chemical class 0.000 title description 35
- 238000000034 method Methods 0.000 title description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 64
- 239000000203 mixture Substances 0.000 description 31
- 229910001507 metal halide Inorganic materials 0.000 description 25
- 150000005309 metal halides Chemical class 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 19
- 229910052736 halogen Inorganic materials 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 238000009835 boiling Methods 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 12
- 150000004820 halides Chemical class 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 8
- 229960003750 ethyl chloride Drugs 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- -1 phosphorus halides Chemical class 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 101150111329 ACE-1 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
Definitions
- My present invention relates to the preparation of alkyl halides and more particularly to the preparation of alkyl halides from ethers.
- the principal object of my invention is to provide an improvedmethod for preparing alkyl halides from aliphatic ethers, which I have found to be readily reactedupon by halogen acids in the presence of certain metalhalides to give nearly quantitative yields of the corresponding halides, when the procedure defined herein is followed.
- the metal halides which are found to be particularly useful for this purpose are the anhydrous halogen salts of zinc, ferric iron, aluminum, and the like.
- the particular halogen salt used depends upon the particular halogenacid used in the process; for example, when I use hydrogen chloride for making an alkvl chloride, a metal chloride such as zinc chloride, ferric chloride,
- ethers from any suitable source may be used, I particularly contemplate the use of ethers formed in the syntheses of alcohols from the corresponding oleflnes.
- oleflnes such as ethylene
- alkyl hydrogen sulphates such. as ethyl hydrogen sulphate
- My process is particularly adapted to be used in conjunction with such a process which produces impure ether as a by-product, the ether thus being saved and treated to form derivatives of the alcohol formed in the main process.
- the temperature a of the mixture below the boiling point of the ether which is beingconverted and preferably below the boiling point of the alkyl halides being formed it is desirable to maintain the temperature below the boiling point of the ether so as 95 to obtain the most eflicient conversion thereof as, during the reaction, the ether should be admixed with and, brought into intimate contact with the metal halides.
- the metal halides used appear to act as catalytic agents. It is-generally o advantageous to maintainthe temperature of the mixture below the boiling point of the halide formed as this permits more ready handling of the mixture and the use of less expensive and complicated apparatus and causes the ether to be more completely converted.
- a still further method of carrying my invention into eifect and one which has been very satisfactory in practice comprises passing a mixture of the ether vapor and the halogen acid gas through a. tower loosely packed with lumps of the metal halide.
- the .lumps of the salt present large contact surfaces and all portions of the mixed gases are brought into contact with them.
- This method is particularly adapted for continuous operation as, when the metal salt has absorbed suflicient moisture to cause it to become inactive, it is merely necessary to pass the gases to another tower containing fresh salt.
- the salt in the tower which has become inactive may then be dehydrated.
- the tower containing the dehydrated salt may then be used to replace the second tower when the salt in it has become rendered inactive by the absorption of moisture.
- Method of preparing an alkyl halide comprising reacting an aliphatic ether with a halogen acid in the presence of a metal halide at a temperature below the boiling point of thealkyl halide and at the close of the reaction separating the alkyl halide.
- the method of preparing an alkyl halide which comprises reacting an aliphatic ether with a halogen acid and an anhydrous metal halide at a temperature below that which is suflicient to drive off water of reaction from the metal, halide.
- the method of preparingan alkyl halide which comprises reacting an aliphatic ether with an anhydrous halogen acid and a metal halide at atemperature below that which is sufllcient to drive ofi water of reaction from the metal halide.
- Method of making an alkyl halide comprising continuously passing a mixture of the vapor of an aliphatic ether and a halogen acid as through a contact zone containing a metal halide presenting an extended surface, at a temperature below that which is sufiicient to drive ofi water of reaction from the metal halide, and recovering the alkyl halide.
- Method of making ethyl chloride comprising passing hydrogen chloride gas into a mixture of ethyl ether and an anhydrous metal halide maintaining the temperature of the mixture below the boiling point of ethyl 'ether, at the close of the reaction distilling off the ethyl chloride, and collecting the same.
- Method of making ethyl chloride comprisin: pa sing dry hydrogen chloride gas into a mixture of ethyl ether and an anhydrous metal halide. until substantially two molecular propor- 17.
- Method of preparing an alkyl halide which tom of hydrogen chloride with respect to the comprises reacting an aliphatic ether with a haloether have been added, maintaining the tempergen acid in the presence 0! a dehydrating metal ature oi the mixture below the boiling point of halide at a temperature below that which is sum- 5 ethyl chloride, thereafter warming the mixture to cient to drive 01! water of reaction from the distill the ethyl chloride. washing the ethyl chlometal halide. ride in the gaseous state, and purifyim; the same BENJAMIN T. BROOKS.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Oct. 1, 1935 by mesne assignments, to Standard 'Alcohol Company, Wilmington, Del., a corporation of Delaware No Drawing.
Application October 1, 1931, Serial No. 566,321
11 Claims. (01. ace-1 2) My present invention relates to the preparation of alkyl halides and more particularly to the preparation of alkyl halides from ethers.
Heretofore, it has been proposed to prepare 5 alkyl halides from the corresponding alcohols and usually by the treatment of the alcohol with phosphorus halides such as phosphorus trichloride, phosphorus penta-chloride or phosphorus tri-bromide or by the distillation of an alcohol with a concentrated halogen acid usually in the presence of sulphuric acid, or other catalyst. It has also been proposed to treat parafiin hydrocarbons with chlorine-for the preparation of the corresponding halides. In the use of such methods, it is generally necessary to use a sub stantial amount of heat and complicated and expensive apparatus which make-the process and the product objectionably expensive.
The principal object of my invention is to provide an improvedmethod for preparing alkyl halides from aliphatic ethers, which I have found to be readily reactedupon by halogen acids in the presence of certain metalhalides to give nearly quantitative yields of the corresponding halides, when the procedure defined herein is followed.
The metal halides which are found to be particularly useful for this purpose are the anhydrous halogen salts of zinc, ferric iron, aluminum, and the like. The particular halogen salt used depends upon the particular halogenacid used in the process; for example, when I use hydrogen chloride for making an alkvl chloride, a metal chloride such as zinc chloride, ferric chloride,
aluminum chloride and the like is used.
While ethers from any suitable source may be used, I particularly contemplate the use of ethers formed in the syntheses of alcohols from the corresponding oleflnes. In such syntheses, oleflnes, such as ethylene, are absorbed in sulphuric acid which is then diluted and the alkyl hydrogen sulphates, such. as ethyl hydrogen sulphate, formed are distilled oils In such a process, large proportions of impure alkyl ethers are produced unless the alkyl hydrogen sulphate is exceedingly highly diluted. My process is particularly adapted to be used in conjunction with such a process which produces impure ether as a by-product, the ether thus being saved and treated to form derivatives of the alcohol formed in the main process. I
Referring more particularly to my preferred method of carrying out the present invention when treatingethyl ether, dry hydrogen chloride gas is passed into a cool mixture of ethyl ether and anhydrous zinc chloride, until substantially two molecular proportions of hydrogen chloride have been added. When the reaction is complete. the mixture is gently warmed and the ethyl 1o chloride distilled oil. The .ethyl chloride produced is washed with water to remove hydrogen chloride and traces of ethyl alcohol. Due to its low boiling point, the ethyl chloride may be washed while in the gaseous state. The washed 15 ethyl chloride is finally subjected to a fractional distillation to remove small proportions of unchanged ethyl ether.
In using the process as above described it is generally necessary to maintain, the temperature a of the mixture below the boiling point of the ether which is beingconverted and preferably below the boiling point of the alkyl halides being formed. It is desirable to maintain the temperature below the boiling point of the ether so as 95 to obtain the most eflicient conversion thereof as, during the reaction, the ether should be admixed with and, brought into intimate contact with the metal halides. The metal halides used appear to act as catalytic agents. It is-generally o advantageous to maintainthe temperature of the mixture below the boiling point of the halide formed as this permits more ready handling of the mixture and the use of less expensive and complicated apparatus and causes the ether to be more completely converted.
While ethers are well known for their chemical stability, I have found that the reaction in my process proceeds rapidly and smoothly at the low temperatures specified. Water is formed during the reaction and'is absorbed by the metal salt, eventually rendering the salt inactive. The salt must then be dehydrated before it can be used to treat a newbatch 'of material.
is also adapted for operatiorias a continuous! process such as by passing halogen acid gas through a stream of the ether carrying the metal halide in suspension or by spraying the ether and metal halide into a stream of the halogen acid gas or by other similar processes.
A still further method of carrying my invention into eifect and one which has been very satisfactory in practice comprises passing a mixture of the ether vapor and the halogen acid gas through a. tower loosely packed with lumps of the metal halide. The .lumps of the salt present large contact surfaces and all portions of the mixed gases are brought into contact with them. In using this process, it is not necessary to take any special precautions to cool the tower or the contents thereof as the ether is in vapor form and readily contacts with the salts in the tower as it passes therethrough. This method is particularly adapted for continuous operation as, when the metal salt has absorbed suflicient moisture to cause it to become inactive, it is merely necessary to pass the gases to another tower containing fresh salt. The salt in the tower which has become inactive may then be dehydrated. The tower containing the dehydrated salt may then be used to replace the second tower when the salt in it has become rendered inactive by the absorption of moisture.
While I have described specific methods of carrying out my process using hydrogen chloride and zinc chloride in the treatment of ethyl ether, it is to be understood that such description is merely by way of illustration and myinvention relates generally to the preparation of alkyl halides and may be used in treating other ethers and substituting other halogen acids and other halogen metal salts than those particularly set out in the example given.
It will be readily apparent to those skilled in the art that many changes and modifications may be made in my invention and the methods herein described for carrying the same into effect without, however, departing from the spirit thereof or the scope of the following claims. Accordingly, my invention as set out in the claims is to be interpreted in the broadest sense permissible in view of the prior art.
1. Method of preparing an alkyl halide comprising reacting an aliphatic ether with a halogen acid in the presence of a metal halide at a temperature below the boiling point of thealkyl halide and at the close of the reaction separating the alkyl halide.
2. The method of preparing an alkyl halide which comprises reacting an aliphatic ether with an anhydrous halogen acid and an anhydrous metal halide at a temperature below the boiling point of the resulting alkyl halide.
3. The method of preparing an alkyl halide which comprises passing halogen-acid-gas through a mixture of liquid ethyl ether and a metal halide. i
4. The method of preparing an alkyl halide which comprises passing halogen-acid-gas through a mixture of ethyl ether and a metal halide and maintaining the mixture during the reaction at a temperature below that which is suflicient to drive on water of reaction from the metal halide.
5. The method of preparing an alkyl halide which comprises passing halogen-acid-gas through a mixture of ethyl ether and a metal halide and maintaining the'mixture at a temperature below thboiling point of the etherduring the reaction.
6. The method of preparing an alkyl halide which comprises passing halogen-acid-gas through a mixture of ethyl ether and a metal 5 halide and maintaining themixture at temperatures below the boiling point of the resulting alkyl halide during the reaction.
I. The method of preparing an alkyl halide which comprises passinghalogen-acid-gas 10 through a mixture of 4 ethyl ether and a metal halide maintaining the mixture at temperatures below the boiling point of the resulting alkyl halide during the reaction, and separating alkyl halide from the resulting mixture. 15
8. The method of preparing an alkyl halide. which comprises passing halogen-acidgas through a mixture of ethyl ether and a metal halide, maintaining the mixture at temperatures below the boiling point of the resulting alkyl 20 halide, separating alkyl halide from the resulting mixture, and washing said alkyl halide with water.
9. The method of' preparing an alkyl halide which comprises passing halogen-acid-gas 25 through a mixture of ethyl ether and a metal halide, maintaining the mixture at temperatures below the boiling point of the resulting alkylhalide during the reaction, separating impure allwl halide from the resulting mixture, and washing 80 .the separated alkyl halide in the gaseous state with water. I
10. The method of preparing an alkyl halide which comprises passing halogen acid gas through a mixture of ethyl ether and a metal 85'.
halide, maintaining the mixture at temperatures below the boiling point of the resulting alkyl halide during the reaction, separating impure alkyl halide from the resulting mixture, and washing said alkyl halide with water at room tempera- 40' tures.
11. The method of preparing an alkyl halide which comprises passing a mixture of ether and halogen acid into contact with an anhydrous metal halide at a temperature below that which is sufiicient to drive ofi water of reaction from the metal halide.
12. The method of preparing an alkyl halide which comprises reacting an aliphatic ether with a halogen acid and an anhydrous metal halide at a temperature below that which is suflicient to drive off water of reaction from the metal, halide.
13. The method of preparingan alkyl halide which comprises reacting an aliphatic ether with an anhydrous halogen acid and a metal halide at atemperature below that which is sufllcient to drive ofi water of reaction from the metal halide.
14. Method of making an alkyl halide, comprising continuously passing a mixture of the vapor of an aliphatic ether and a halogen acid as through a contact zone containing a metal halide presenting an extended surface, at a temperature below that which is sufiicient to drive ofi water of reaction from the metal halide, and recovering the alkyl halide.
15. Method of making ethyl chloride, comprising passing hydrogen chloride gas into a mixture of ethyl ether and an anhydrous metal halide maintaining the temperature of the mixture below the boiling point of ethyl 'ether, at the close of the reaction distilling off the ethyl chloride, and collecting the same. v
16. Method of making ethyl chloride, comprisin: pa sing dry hydrogen chloride gas into a mixture of ethyl ether and an anhydrous metal halide. until substantially two molecular propor- 17. Method of preparing an alkyl halide which tom of hydrogen chloride with respect to the comprises reacting an aliphatic ether with a haloether have been added, maintaining the tempergen acid in the presence 0! a dehydrating metal ature oi the mixture below the boiling point of halide at a temperature below that which is sum- 5 ethyl chloride, thereafter warming the mixture to cient to drive 01! water of reaction from the distill the ethyl chloride. washing the ethyl chlometal halide. ride in the gaseous state, and purifyim; the same BENJAMIN T. BROOKS.
byiractionaldistillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US566321A US2015706A (en) | 1931-10-01 | 1931-10-01 | Process for making alkyl halides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US566321A US2015706A (en) | 1931-10-01 | 1931-10-01 | Process for making alkyl halides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2015706A true US2015706A (en) | 1935-10-01 |
Family
ID=24262405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US566321A Expired - Lifetime US2015706A (en) | 1931-10-01 | 1931-10-01 | Process for making alkyl halides |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2015706A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2421090A (en) * | 1942-08-01 | 1947-05-27 | Univ Minnesota | Long chain aliphatic halides and method of preparing same |
| US3203978A (en) * | 1961-06-06 | 1965-08-31 | Montedison Spa | Process for preparing the methyl ester of 2, 5-hexadienoic acid |
| US3432561A (en) * | 1966-03-28 | 1969-03-11 | Baird Chem Ind | Preparation of alkyl chlorides by the reaction of alkyl alcohols with phosphorus trichloride |
-
1931
- 1931-10-01 US US566321A patent/US2015706A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2421090A (en) * | 1942-08-01 | 1947-05-27 | Univ Minnesota | Long chain aliphatic halides and method of preparing same |
| US3203978A (en) * | 1961-06-06 | 1965-08-31 | Montedison Spa | Process for preparing the methyl ester of 2, 5-hexadienoic acid |
| US3432561A (en) * | 1966-03-28 | 1969-03-11 | Baird Chem Ind | Preparation of alkyl chlorides by the reaction of alkyl alcohols with phosphorus trichloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2015706A (en) | Process for making alkyl halides | |
| US2357095A (en) | Process for the manufacture of anhydrous hydrogen halide | |
| US2174756A (en) | Production of unsaturated aliphatic or cycloaliphatic carboxylic acid nitriles | |
| US2406195A (en) | Manufacture of the higher chlorides of methane | |
| US2489316A (en) | Manufacture of sulfonic anhydrides | |
| US2392303A (en) | Production of acrylic nitrile | |
| US2050442A (en) | Manufacture of ethyl alcohol | |
| US1765688A (en) | Process of making sulphuryl chloride | |
| US2079652A (en) | Manufacture of esters from olefines | |
| US2281762A (en) | Process of producing sulphur trioxide and oxygen | |
| US2416011A (en) | Recovery of sulphur dioxide-free hydrochloric acid from aluminum chloride sludge | |
| US2296763A (en) | Process for the production of chlorine and metal nitrate | |
| US1999576A (en) | Production of glyoxals | |
| US2521113A (en) | Process for the synthesis of vinyl esters of carboxylic acids | |
| US2014850A (en) | Manufacture of carboxylic acid esters from olefines | |
| US1914425A (en) | Process of dehydrating fluorine compounds | |
| US1845665A (en) | Purification of alcohols | |
| US2360492A (en) | Process of producing alkali metal and alkaline earth metal hypochlorites and alcohol | |
| US3080437A (en) | Copper salt slurry process for diolefin separation | |
| US2386798A (en) | Recovery of catalysts | |
| US2425582A (en) | Production of nitrous oxide | |
| US2270705A (en) | Production of acrolein | |
| US2244324A (en) | Process for the production of an alkyl bromide | |
| US2007478A (en) | Production of nitrates from metal halides | |
| US1632485A (en) | Manufacture of hypochlorites |